Gas separation membranes based on perfluorinated polymers

ABSTRACT

Disclosed herein is a process for separating components of a gas mixture using gas-separation copolymer membranes. These membranes use a selective layer made from copolymers of perfluorodioxolane monomers. The resulting membranes have superior selectivity performance for gas pairs of interest while maintaining fast gas permeance compared to membranes prepared using conventional perfluoropolymers, such as Teflon® AF, Hyflon® AD, and Cytop®.

FIELD OF THE INVENTION

The invention relates to membrane-based gas separation processes. Inparticular, the invention relates to gas separation processes usingcopolymer membranes containing perfluorodioxolane monomers.

BACKGROUND OF THE INVENTION

Presented below is background information on certain aspects of thepresent invention as they may relate to technical features referred toin the detailed description, but not necessarily described in detail.The discussion below should not be construed as an admission as to therelevance of the information to the claimed invention or the prior arteffect of the material described.

The search for a membrane for use in gas separation applications thatcombines high selectivity with high flux continues. Currentperfluoropolymer membranes, such as Hyflon® AD (Solvay), Teflon® AF (DuPont), Cytop® (Asahi Glass), and variants thereof, have excellentchemical resistance and stability. We reported earlier, in U.S. Pat. No.6,361,583, membranes that are made from glassy polymers or copolymers,including Hyflon® AD, and are characterized by having repeating units ofa fluorinated, cyclic structure. In general, the ring structures inthese materials frustrate polymer chain packing yielding amorphouspolymers with relatively high gas permeability. These developedmembranes are also more resistant to plasticization by hydrocarbons thanprior art membranes and are able to recover from accidental exposure toliquid hydrocarbons.

It is known that copolymerization of fluorinated cyclic monomers withtetrafluoroethylene (TFE) enhances the chemical resistance and physicalrigidity of membranes. TFE is also known to improve processability andhas the effect of lowering gas permeability and increasing sizeselectivity in Hyflon® AD and Teflon® AF. Therefore, combinations of TFEwith other monomer units, in particular perfluorinated dioxoles, such asTeflon® AF and Hyflon® AD, that result in overall amorphous, yet rigid,highly fluorinated, copolymers are preferred for industrial membraneapplications. However, a drawback to these membranes is that theirselectivities are relatively low for a number of gas pairs of interest,including H₂/CH₄, He/CH₄, CO₂/CH₄, and N₂/CH₄.

Other than the commercially available perfluoropolymers, there is verylimited gas transport data available for fully fluorinated polymers.Paul and Chio, “Gas permeation in a dry Nafion membrane,” Industrial &Engineering Chemistry Research, 27, 2161-2164 (1988), examined gastransport in dry Nafion® (an ionic copolymer of TFE and sulfonatedperfluorovinyl ether) and found relatively high permeabilities andselectivities for several gas pairs (He/CH₄, He/H₂, and N₂/CH₄) comparedto conventional hydrocarbon-based polymers considered for membraneapplications. Nafion® and related ionic materials are used to make ionexchange membranes for electrochemical cells and the like. Because oftheir high cost and need for carefully controlled operating conditions,such as adjusting the relative humidity of the feed gas to preventpolymer swelling and loss of performance, these ionic membranes are notsuitable for industrial gas separations.

Despite the improvements described above, there remains a need forbetter gas separation membranes, and specifically for improved membranescombining high flux, high selectivity, and good chemical resistance.

Recently, there have been reports of a new class of non-ionic amorphousperfluoropolymers. U.S. Pat. Nos. 7,582,714; 7,635,780; 7,754,901; and8,168,808, all to Yoshiyuki Okamoto, disclose compositions and processesfor making perfluoro-2-methylene-1,3-dioxolane derivatives.

Yang et al., “Novel Amorphous Perfluorocopolymeric System: Copolymers ofPerfluoro-2-methylene-1,3-dioxolane Derivatives,” Journal of PolymerScience: Part A: Polymer Chemistry, Vol. 44, 1613-1618 (2006), andOkamoto et al., “Synthesis and properties of amorphous perfluorinatedpolymers,” Chemistry Today, vol. 27, n. 4, pp. 46-48 (July-August 2009),disclose the copolymerization of two dioxolane derivatives,perfluorotetrahydro-2-methylene-furo[3,4,-d][1,3]dioxolane andperfluoro-2-methylene-4-methoxymethyl-1,3-dioxolane. The copolymers werefound to be thermally stable, have low refractive indices, and highoptical transparency from UV to near-infrared, making them idealcandidates for use in optical and electrical materials.

U.S. Pat. No. 3,308,107, to Du Pont, discloses a similar dioxolanederivative, perfluoro-2-methylene-4-methyl-1,3-dioxolane. Homopolymersand copolymers of perfluoro-2-methylene-4-methyl-1,3-dioxolane with TFEare also disclosed.

U.S. Pat. No. 5,051,114, also to Du Pont, discloses the testing ofpoly-[perfluoro-2-methylene-4-methyl-1,3-dioxolane] for use in amembrane for gas separation. The results indicated that this materialexhibited gas permeabilities 2.5 to 40 times lower as compared todipolymer membranes of perfluoro-2,2-dimethyl-1,3-dioxole and TFE, buthad higher selectivities.

To date, however, there have been no studies using copolymers of theperfluoropolymers described by Yang et al. and Okamoto et al. inmembranes for gas separation processes.

SUMMARY OF THE INVENTION

The present invention relates to a process for separating components ofa gas mixture whereby the gas mixture is passed across an improvedseparation membrane having a selective layer formed from a copolymer ofperfluorodioxolane monomers.

In a basic embodiment, the invention is a process for separating twocomponents, A and B, of a gas mixture, comprising:

-   -   (a) passing the gas mixture across a separation membrane having        a feed side and a permeate side, the separation membrane having        a selective layer comprising a copolymer comprising at least two        perfluorodioxolane monomers;    -   (b) providing a driving force for transmembrane permeation;    -   (c) withdrawing from the permeate side a permeate stream        enriched in component A compared to the gas mixture;    -   (d) withdrawing from the feed side a residue stream depleted in        component A compared to the gas mixture.

Membranes previously developed for gas separation processes haveincorporated the use of amorphous homopolymers of perfluorinateddioxoles, dioxolanes, or cyclic acid ethers, or copolymers of these withtetrafluoroethylene. However, the use of TFE results in membranes thatlack high selectivities for components of a gas mixture.

To address these performance issues, particularly preferred materialsfor the selective layer of the membrane used to carry out the process ofthe invention are perfluorodioxolane monomers selected from the groupconsisting of the structures found in Table 1, below:

TABLE 1 Perfluorodioxolane Monomers

Perfluorotetrahydro-2- Perfluoro-2-methylene- methylene-furo[3,4-4-methy1-1,3,- d][1,3]-dioxolane dioxolane (Monomer A) (Monomer B)

Perfluoro-2-methylene- Perfluoro-2-methylene- 4-methoxymethyl-4,5-dimethy1-1,3,- 1,3-dioxolane dioxolane (Monomer C) (Monomer D)

Perfluoro-3-methylene- Perfluoro-3-methylene- 2,4-dioxabicyclo-2,3-dioxabicyclo- [4,3,0]nonane [3,3,0] octane (Monomer E) (Monomer F)

Perfluoro-2-methylene- Perfluoro-2-methylene- 4,5-dimethoxymethyl-1,3-dioxolane 1,3-dioxolane (Monomer H) (Monomer G)

An important advantage of the present invention is that use ofperfluorinated dioxolane copolymers in the membrane can result in higherselectivity for desired gases than can be obtained using prior artmembranes that incorporate TFE or cyclic perfluorinated homopolymers.

In another embodiment, the present invention relates to a process forseparating two components, A and B, of a gas mixture, comprising:

-   -   (a) passing the gas mixture across a separation membrane having        a feed side and a permeate side, the separation membrane having        a selective layer comprising a copolymer formed from a first        perfluorodioxolane monomer having the formula

-   -    and        -   a second perfluorodioxolane monomer selected from the group            consisting of the structures found in Table 1 with the            exception of Monomer H.    -   (b) providing a driving force for transmembrane permeation;    -   (c) withdrawing from the permeate side a permeate stream        enriched in component A compared to the gas mixture; and    -   (d) withdrawing from the feed side a residue stream depleted in        component A compared to the gas mixture.

Representative membranes having particularly high selectivity are thoseformed from perfluoro-2-methylene-1,3-dioxolane andperfluoro-2-methylene-4,5-dimethyl-1,3-dioxolane. Thus, a most preferredcopolymer is one having the structure:

-   -   where m and n are positive integers.

In certain aspects, the copolymer is a dipolymer containing at least 25mol % or greater of perfluoro-2-methylene-1,3-dioxolane.

Due to their advantageous properties, the membranes and processes of theinvention are useful for many gas separation applications. Specificexamples include, but are not limited to the separation of variousgases, for example, nitrogen, helium, carbon dioxide, and hydrogen frommethane.

The gas mixture may contain at least two components, designatedcomponent A and component B, that are to be separated from each otherand optionally another component or components in the stream. Thepermeating desired gas may be either a valuable gas that is desired toretrieve as an enriched product, or a contaminant that is desired toremove. Thus, either the permeate stream or the residue stream, or both,may be the useful products of the process.

In certain aspects, the invention is a process for separating twocomponents, A and B, of a gas mixture wherein component A is hydrogenand component B is methane. Such a mixture may be found in a steamreforming process. For example, the process of the invention may be usedto recover hydrogen from synthesis gas, to remove carbon dioxide fromsynthesis gas, or to adjust the ratio of hydrogen to carbon monoxide insynthesis gas.

In certain aspects, the invention is a process for separating twocomponents, A and B, of a gas mixture wherein component A is carbondioxide and component B is methane. This process may be involved incarbon capture and storage or used in the separation of CO₂ from naturalgas.

In other aspects, the invention is a process for separating twocomponents, A and B, of a gas mixture wherein component A is nitrogenand component B is methane. This process may be involved in removingnitrogen from nitrogen-contaminated natural gas.

In yet another aspect, the invention is a process for separating twocomponents, A and B, of a gas mixture wherein component A is helium andcomponent B is methane. This process may be useful for producing heliumthrough natural gas extraction and subsequent purification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing pure gas H₂ permeance and H₂/CH₄ selectivityas a function of Monomer H content for membranes with selective layerscomposed of copolymers of Monomers D and H (Polymers 443, 444, and 445).

FIG. 2 is a graph showing H₂/CH₄ selectivity as a function of H₂permeance for membranes made from commercial perfluoropolymers (Cytop®,Hyflon® AD, and Teflon® AF) and Polymers 443, 444, and 445.

FIG. 3 is a graph showing N₂/CH₄ selectivity as a function of N₂permeance for membranes made from commercial perfluoropolymers (Cytop®,Hyflon® AD, and Teflon® AF) and Polymers 443, 444, and 445.

FIG. 4 is a graph showing He/CH₄ selectivity as a function of Hepermeance for membranes made from commercial perfluoropolymers (Cytop®,Hyflon® AD, and Teflon® AF) and Polymers 443, 444, and 445.

FIG. 5 is a graph showing CO₂/CH₄ selectivity as a function of CO₂permeance for membranes made from commercial perfluoropolymers (Cytop®,Hyflon® AD, and Teflon® AF) and Polymers 443, 444, and 445.

DETAILED DESCRIPTION OF THE INVENTION

The term “gas” as used herein means a gas or a vapor.

The term “polymer” as used herein generally includes, but is not limitedto, homopolymers, copolymers, such as for example, block, graft, randomand alternating copolymers, terpolymers, etc. and blends andmodifications thereof. Furthermore, unless otherwise specificallylimited, the term “polymer” shall include all possible geometricalconfigurations of the material. These configurations include, but arenot limited to, isotactic and atactic symmetries.

The term “highly fluorinated” as used herein means that at least 90% ofthe total number of halogen and hydrogen atoms attached to the polymerbackbone and side chains are fluorine atoms.

The terms “fully-fluorinated” and “perfluorinated” as used herein areinterchangeable and refer to a compound where all of the availablehydrogen bonded to carbon have been replaced by fluorine.

All percentages herein are by volume unless otherwise stated.

The invention relates to a process for separating two components, A andB, of a gas mixture. The separation is carried out by running a streamof the gas mixture across a membrane that is selective for the desiredcomponent to be separated from another component. The desired componentto be separated into the permeate may be either Component A or ComponentB. The process results, therefore, in a permeate stream enriched in thedesired component and a residue stream depleted in that component.

In a basic embodiment, the process of the invention includes thefollowing steps:

(a) passing the gas mixture across a separation membrane having a feedside and a permeate side, the separation membrane having a selectivelayer comprising a copolymer formed from at least two perfluorodioxolanemonomers;

(b) providing a driving force for transmembrane permeation;

(c) withdrawing from the permeate side a permeate stream enriched incomponent A compared to the gas mixture;

(d) withdrawing from the feed side a residue stream depleted incomponent A compared to the gas mixture.

At least the selective layer responsible for the gas discriminatingproperties of the membrane is made from a glassy copolymer. Thecopolymer should be substantially amorphous. Crystalline polymers aretypically essentially insoluble and thus render membrane makingdifficult, as well as exhibiting generally very low gas permeabilities.Crystalline polymers are not normally suitable for the selective layer,therefore.

The selective layer copolymer should be fluorinated, and generally thedegree of fluorination should be high to increase the chemical inertnessand resistance of the material. By high, we mean having afluorine:carbon ratio of atoms in the polymer of at least 1:1. Mostpreferably, the polymer is perfluorinated, even if the perfluorinatedstructure has less than a 1:1 fluorine:carbon ratio.

Various materials may be used for the copolymeric selective layer tomeet the characterizing requirements. These include copolymerscomprising perfluorinated dioxolane monomers.

The perfluorinated dioxolane monomers as described herein arecharacterized by a 1,3-dioxolane ring, having the general form:

Preferred monomers may be selected fromperfluoro-2-methylene-1,3-dioxolane or derivatives thereof containingvarious substituent groups at the fourth and fifth positions of thedioxolane ring. These monomers are represented by the structures foundin Table 1, above.

None of the structures in Table 1 are new monomers in themselves.Generally, dioxolanes can be prepared by acetalization of aldehydes andketalization of ketones with ethylene glycol. Formulations embracingthose suitable for use in the invention are described in U.S. Pat. Nos.3,308,107; 5,051,114; 7,754,901; 7,635,780; and 8,168,808, incorporatedherein by reference. The homopolymers of the monomers in Table 1 may beprepared by direct fluorination of hydrocarbon precursors andpolymerized using perfluoro dibenzoyl peroxide as a free radicalinitiator to yield a linear polymer. The resulting polymers are solublein fluorinated solvents, such as hexafluorobenzene, perfluoro-hexane,and fluorinated FC43 (3M™). Copolymerization of the monomers in Table 1may also be carried out in bulk and in a hexafluorobenzene solutionusing perfluoro dibenzoyl peroxide.

In a preferred embodiment, the selective layer comprises a copolymer ofthe perfluorodioxolane monomers found in Table 1. Thus, the separationmembrane may have a selective layer comprising a copolymer formed from afirst perfluorodioxolane monomer and a second, differentperfluorodioxolane monomer. Any combination of perfluorodioxolanemonomers found in Table 1 may be used.

A homopolymer of perfluoro-2-methylene-1,3-dioxolane (Monomer H) iscrystalline in nature, which was confirmed by Mike{hacek over (s)} etal., “Characterization and Properties of Semicrystalline and AmorphousPerfluoropolymer: poly(perfluoro-2-methylene-1,3-dioxolane),” Polymersfor Advanced Technologies, v. 22, pp. 1272-1277 (2011). Thiscrystallinity reflects the ability of the repeat unit in the homopolymerof Monomer H to pack tightly, forming ordered structures. As a result,Monomer H does not dissolve in fluorinated solvents. However, asdescribed herein, copolymerizing Monomer H with another dioxolanemonomer from Table 1 in the appropriate amounts results in an amorphousstructure, which is desirable for gas separation membrane materials.

In other embodiments, the copolymer may comprise more than twoperfluorodioxolane monomers.

In a more preferred embodiment, the separation membrane has a selectivelayer comprising a copolymer formed from a first perfluorodioxolanemonomer having the formula

and a second perfluorodioxolane monomer having the formula

where R and R′ are fluorine and/or alkylfluoro groups.

Preferably, in some embodiments, the separation membrane has a selectivelayer comprising a copolymer formed from a first perfluorodioxolanemonomer having the formula

and a second perfluorodioxolane monomer selected from Table 1, whereinthe second perfluorodioxolane monomer is not Monomer H.

Unlike Monomer H, Monomer D is more bulky and frustrates polymer chainpacking, yielding a selective layer with higher free volume and highergas permeability. Thus, in a most preferred embodiment, the copolymercomprises monomers of perfluoro-2-methylene-1,3-dioxolane (Monomer H)and perfluoro-2-methylene-4,5-dimethyl-1,3,-dioxolane (Monomer D).

When any pair of monomers is used, one will tend to be more denselypacked and perhaps crystalline than the other, and the respectiveproportions of the two monomers will alter the membrane properties. As arepresentative, non-limiting example, FIG. 1 shows the effect of theratio of Monomers D and H on the performance of the resulting gasseparation membrane. An appropriate amount of Monomer D (or anothermonomer from Table 1 other than Monomer H) is required to yield anamorphous copolymer with Monomer H. However, an appropriate amount ofMonomer H is required to yield copolymers with high selectivity; toomuch of Monomer D (or another monomer from Table 1 other than Monomer H)results in an amorphous copolymer with relatively low gas selectivity.

Within the range of amorphous copolymers of D and H, there is atrade-off between permeance and selectivity. Relatively largeproportions of D increase permeance at the expense of selectivity, andrelatively large proportions of H increase selectivity at the expense ofpermeance. A preferred proportion of Monomer H is at least 25 mol %,more preferably at least 40 mol %, and most preferable at least 55 mol%.

Thus, the preferred copolymer has just enough of Monomer D, or in adifferent embodiment, another monomer selected from Table 1 other thanMonomer H, to give an amorphous copolymer, but retains enough of MonomerH to yield high gas selectivity.

With the perfluoropolymers described herein, the bonding of the monomersoccurs outside the main dioxolane ring. This process is different thandioxole polymerization, which polymerize by the opening of a double bondwithin a five-member ring.

Copolymerization of the perfluoromonomers is represented by thefollowing exemplary formula:

where m and n are positive integers.

In a preferred embodiment, the copolymer is an ideal random copolymer.

In yet another embodiment, the selective layer of the separationmembrane may comprise a copolymer formed from a perfluorodioxolanemonomer selected from the group consisting of the structures found inTable 1 and a perfluorodioxole monomer, such as Teflon® AF and Hyflon®AD, or a polyperfluoro (alkenyl vinyl ether) monomer, such as Cytop®.

The copolymer chosen for the selective layer can be used to form filmsor membranes by any convenient technique known in the art, and may takediverse forms. Because the polymers are glassy and rigid, an unsupportedfilm, tube or fiber of the polymer may be usable in principle as asingle-layer membrane. However, such single-layer films will normally betoo thick to yield acceptable transmembrane flux, and in practice, theseparation membrane usually comprises a very thin selective layer thatforms part of a thicker structure. This may be, for example, an integralasymmetric membrane, comprising a dense skin region that forms theselective layer and a microporous support region. Such membranes wereoriginally developed by Loeb and Sourirajan, and their preparation inflat sheet or hollow fiber form is now conventional in the art and isdescribed, for example, in U.S. Pat. No. 3,133,132 to Loeb, and U.S.Pat. No. 4,230,463 to Henis and Tripodi.

As a further, and a preferred, alternative, the membrane may be acomposite membrane, that is, a membrane having multiple layers. Moderncomposite membranes typically comprise a highly permeable but relativelynon-selective support membrane, which provides mechanical strength,coated with a thin selective layer of another material that is primarilyresponsible for the separation properties. Typically, but notnecessarily, such a composite membrane is made by solution-casting thesupport membrane, then solution-coating the selective layer. Generalpreparation techniques for making composite membranes of this type arewell known, and are described, for example, in U.S. Pat. No. 4,243,701to Riley et al., incorporated herein by reference.

Again, the membrane may take flat-sheet, tube or hollow-fiber form. Themost preferred support membranes are those with an asymmetric structure,which provides a smooth, comparatively dense surface on which to coatthe selective layer. Support membranes are themselves frequently castonto a backing web of paper or fabric. As an alternative to coating ontoa support membrane, it is also possible to make a composite membrane bysolution-casting the polymer directly onto a non-removable backing web,as mentioned above. In hollow-fiber form, multilayer composite membranesmay be made by a coating procedure as taught, for example, in U.S. Pat.Nos. 4,863,761; 5,242,636; and 5,156,888, or by using a double-capillaryspinneret of the type taught in U.S. Pat. Nos. 5,141,642 and 5,318,417.

A gutter layer may optionally be used between the support membrane andthe selective layer, for example to smooth the support surface andchannel fluid to the support membrane pores. In this case, the supportmembrane is first coated with the gutter layer, then with the perfluoroselective layer as described herein.

Multiple selective layers may also be used.

The thickness of the selective layer or skin of the membranes can bechosen according to the proposed use, but will generally be no thickerthan 5 μm, and typically no thicker than 1 μm. It is preferred that theselective layer be sufficiently thin that the membrane provide apressure-normalized hydrogen flux, as measured with pure hydrogen gas at25° C., of at least about 100 GPU (where 1 GPU=1×10⁻⁶cm³(STP)/cm²·s·cmHg), more preferably at least about 200 GPU and mostpreferably at least about 400 GPU. In a preferred embodiment, theselective layer thickness is no greater than about 0.5 μm, and mostpreferably between about 0.3 μm and 0.5 μm.

Once formed, the membranes exhibit a combination of good mechanicalproperties, thermal stability, and high chemical resistance. Thefluorocarbon polymers that form the selective layer are typicallyinsoluble except in perfluorinated solvents and are resistant to acids,alkalis, oils, low-molecular-weight esters, ethers and ketones,aliphatic and aromatic hydrocarbons, and oxidizing agents, making themsuitable for use not only in the presence of C₃₊ hydrocarbons, but inmany other hostile environments.

The membranes of the invention may be prepared in any known membraneform and housed in any convenient type of housing and separation unit.We prefer to prepare the membranes in flat-sheet form and to house themin spiral-wound modules. However, flat-sheet membranes may also bemounted in plate-and-frame modules or in any other way. If the membranesare prepared in the form of hollow fibers or tubes, they may be pottedin cylindrical housings or otherwise.

The membrane separation unit comprises one or more membrane modules. Thenumber of membrane modules required will vary according to the volume ofgas to be treated, the composition of the feed gas, the desiredcompositions of the permeate and residue streams, the operating pressureof the system, and the available membrane area per module. Systems maycontain as few as one membrane module or as many as several hundred ormore. The modules may be housed individually in pressure vessels ormultiple elements may be mounted together in a sealed housing ofappropriate diameter and length.

Of particular importance, the membranes and processes of the inventionare useful in applications for producing hydrogen or chemicals fromhydrocarbon feedstocks, such as reforming or gasification processesfollowed by separation or chemical synthesis. Steam reforming is wellknown in the chemical processing arts, and involves the formation ofvarious gas mixtures commonly known as synthesis gas or syngas from alight hydrocarbon feedstock, steam and optionally other gases, such asair, oxygen or nitrogen. Synthesis gas usually contains at leasthydrogen, carbon dioxide, carbon monoxide and methane, but the exactcomposition can be varied depending on its intended use.

Plant design and process operating conditions thus differ in theirdetails, but the steam reforming process always includes a basicsteam/hydrocarbon reforming reaction step, carried out at hightemperature and elevated pressure, and one or more subsequent treatmentsof the raw synthesis gas to remove carbon dioxide or make otheradjustments to the gas composition. The processes of the invention areexpected to be especially useful in carrying out such treatments.

In another aspect, the invention is a process for separating carbondioxide from methane, especially if the mixture also contains C₃₊hydrocarbon vapors. Such a mixture might be encountered during theprocessing of natural gas, of associated gas from oil wells, or ofcertain petrochemical streams, for example. The processes of theinvention are expected to be useful as part of the gas treatment train,either in the field or at a gas processing plant, for example.

In another aspect, the invention is a process for recovering helium fromnatural gas. Helium is a rare gas on Earth. Almost all of the commercialhelium requirements are supplied by extraction from helium-containingnatural gas by low temperature fractional distillation processes. Theresulting helium rich gases are further purified or refined usingadditional cryogenic distillation steps or by pressure swing adsorption(PSA) processes which selectively remove other gases. These finalrefining steps result in commercial grades of helium in excess of 99.9%.The processes of the invention are expected to be useful in replacing orsupplementing one or more of the unit operations in the helium recoveryplant.

In yet another aspect, the invention is a process for separatingnitrogen from natural gas. The goal will often be to reduce the nitrogencontent of the natural gas to no more than about 4% nitrogen, which isan acceptable total inerts value for pipeline gas. In othercircumstances, a higher or lower nitrogen target value may be required.Once again, the processes of the invention are expected to be useful infield or plant equipment as stand alone or supplementary units to meetthe desired nitrogen concentration target.

Additionally, in another aspect, the invention is a process forseparating oxygen from nitrogen. Oxygen is used to enhance thecombustion of all fuels, enabling improved burning zone control, andlowering emissions. The present invention is expected to yield enrichedoxygen that can be used advantageously in combustion processes, such askilns, or when using low-grade fuels, where reduction in ballastnitrogen is beneficial.

In a further aspect, the invention is a process for separating waterfrom alcohols, such as ethanol, particularly bioethanol produced fromnatural sources. A major drawback to more economical use of bioethanolas a fuel is the energy used to grow the feedstock, to ferment it, andto separate a dry ethanol product from the fermentation broth. Theprocesses of the invention are expected to be useful in lowering theenergy costs associated with ethanol separation (dehydration).

The invention is now illustrated in further detail by specific examples.These examples are intended to further clarify the invention, and arenot intended to limit the scope in any way.

EXAMPLES Example 1 Membrane Preparation

Composite membranes were prepared using homopolymer and copolymersolutions prepared from the monomers found in Table 2. For Polymers443-445, different compositions (mol %) of Monomers D and H were used.

The perfluoro selective layers were coated onto support membranes,either on a small coater or by hand coating, and the membranes werefinished by oven drying. Samples of each finished composite membranewere then cut into 13.8 cm² stamps.

Example 2 Pure-Gas Testing of the Perfluoro Composite Membranes

The membranes were dried in order to remove any residual solvents andthen tested in a permeation test-cell apparatus with pure gases at roomtemperature, 50 psig feed pressure, and 0 psig permeate pressure. Thegas fluxes of the membranes were measured, and the permeances andselectivities were calculated.

For comparative purposes, tests were also run with membranes havingselective layers made from several formulations of Hyflon® AD, Cytop®,and Teflon® AF.

The results for the different homopolymers and copolymers tested areshown in Table 2, below:

TABLE 2 Pure-Gas Permeation Results Monomer Pure-Gas Permeance (GPU)Pure-Gas Selectivity Sample Composition N₂ H₂ He CO₂ N₂/CH₄ H₂/CH₄He/CH₄ CO₂/CH₄ Polymer 43 mol % D/ 28 695 1,370 256 5.3 129 258 47 44357 mol % H Polymer 58 mol % D/ 41 704 1,250 328 4.2 72 130 34 444 42 mol% H Polymer 74 mol % D/ 54 822 1,410 388 3.2 48 82 23 445 26 mol % HHyflon ® 176 1,730 2,600 1,330 2.4 23 34 18 AD60 Hyflon ® 33 446 1,120268 2.7 36 90 22 AD40 Cytop ® 18 292 788 153 3.0 48 130 25 Teflon ®2,700 10,500 10,500 13,000 1.2 4.6 4.6 5.8 AF2400

From Table 2, in most cases Polymer 443 has better selectivityperformance for pure gas pairs than Hyflon® AD, Cytop®, and Teflon® AF.

Additionally, as can be seen in FIGS. 2-5, Polymer 443 performed wellabove the upper bound tradeoff line defined by the conventionalperfluoropolymer membranes for hydrogen/methane, nitrogen/methane,helium/methane, and carbon dioxide/methane separations.

We claim:
 1. A process for separating two components, A and B, of a gasmixture, comprising: (a) passing the gas mixture across a separationmembrane having a feed side and a permeate side, the separation membranehaving a selective layer comprising a copolymer comprising a firstperfluorodioxolane monomer having the formula

 and a second perfluorodioxolane monomer; (b) providing a driving forcefor transmembrane permeation; (c) withdrawing from the permeate side apermeate stream enriched in component A compared to the gas mixture; and(d) withdrawing from the feed side a residue stream depleted incomponent A compared to the gas mixture.
 2. The process of claim 1,wherein the second perfluorodioxolane monomer is selected from the groupconsisting of:

Perfluorotetrahydro- Perfluoro-2-methylene- 2-methylene-furo[3,4-4-methyl-1,3,- d][1,3]-dioxolane dioxolane (Monomer A) (Monomer B)

Perfluoro-2-methylene- Perfluoro-2-methylene- 4-methoxymethyl-4,5-dimethyl-1,3,- 1,3-dioxolane dioxolane (Monomer C) (Monomer D)

Perfluoro-3-methylene- Perfluoro-3-methylene- 2,4-dioxabicyclo-2,3-dioxabicyclo- [4,3,0]nonane [3,3,0] octane (Monomer E) (Monomer F)

Perfluoro-2-methylene-4,5- dimethoxymethyl-1,3-dioxolane (Monomer G).


3. The process of claim 1, wherein the copolymer comprises monomers ofperfluoro-2-methylene-1,3-dioxolane andperfluoro-2-methylene-4,5-methoxymethyl-1,3-dioxolane.
 4. The process ofclaim 1, wherein component A is chosen from the group consisting ofhydrogen, carbon dioxide, nitrogen, helium and organic compounds.
 5. Theprocess of claim 1, wherein component A is hydrogen.
 6. The process ofclaim 1, wherein component A is carbon dioxide.
 7. The process of claim1, wherein component A is nitrogen.
 8. The process of claim 1, whereincomponent A is helium.
 9. The process of claim 1, wherein component B ismethane.
 10. The process of claim 1, wherein the gas mixture furthercomprises methane and C₃₊ hydrocarbon vapors.
 11. The process of claim1, wherein component A is nitrogen and component B is methane.
 12. Theprocess of claim 1, wherein component A is carbon dioxide and componentB is methane.
 13. The process of claim 1, wherein component A ishydrogen and component B is methane.
 14. The process of claim 1, whereincomponent A is helium and component B is methane.
 15. The process ofclaim 1, wherein the selective layer comprises a copolymer having theformula:

where m and n are positive integers.
 16. The process of claim 1, whereinthe copolymer is a dipolymer containing at least 25 mol % ofperfluoro-2-methylene-1,3-dioxolane.